CN111375274B - Containing SO 2 Gas treatment method and apparatus - Google Patents
Containing SO 2 Gas treatment method and apparatus Download PDFInfo
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- CN111375274B CN111375274B CN201811651651.1A CN201811651651A CN111375274B CN 111375274 B CN111375274 B CN 111375274B CN 201811651651 A CN201811651651 A CN 201811651651A CN 111375274 B CN111375274 B CN 111375274B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
- B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
- B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
Abstract
The invention relates to a method for preparing a sulfur-containing organic compound 2 The gas treating method and apparatus includes treating gas containing SO 2 The gas is compressed in the compression unit and then enters the adsorption unit for adsorption, the adsorption material adopted by the adsorption unit is a modified zinc-based metal organic framework material, and desorption regeneration is performed after adsorption penetration. The invention can realize SO 2 High efficiency physical adsorption without frequent operation, SO 2 High recovery rate and good operation stability, and the purified gas meets the emission requirement.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a sulfur dioxide (SO) -containing catalyst 2 A method and apparatus for treating gas.
Background
Since coal and petroleum generally contain sulfur compounds, SO is formed during combustion 2 Resulting in SO contained in the exhaust gas 2 A gas. SO (SO) 2 The air is colorless and has pungent odor at normal temperature, and is one of the main pollutants in the atmosphere. As early as in the fifteen program, SO 2 Becomes one of the main pollutant emission indexes for national key control of emission. SO in atmospheric pollution emission standard implemented in 7/1 in 2017 2 Is limited to 100mg/m 3 Having individual devices or areas, SO 2 Is required to be less than 50mg/m 3 。
Currently, widely used desulfurization techniques can be classified into wet desulfurization techniques and dry desulfurization techniques. The existing desulfurization technology can be divided into three types according to the recycling degree of desulfurization products: the first type is SO 2 After being removed, the waste water cannot be recycled or is difficult to utilize, such as a gypsum method, a carbide slag method and the like, and the methods generate a large amount of liquid or solid waste and bring secondary pollution. The second is the oxidation of SO by chemical agents or catalytic oxidation 2 Conversion to dilute sulfuric acid or sulfate, e.g. hydrogen peroxide oxidation,Ammonia oxidation and wet activated carbon catalysis, and the use of hydrogen peroxide to remove SO as described in patent CN105381699A 2 Patent CN101085410 describes the treatment of SO in flue gases 2 A method for converting to ammonium sulfate. The technologies need to consume oxidant or catalyst continuously, and relate to the problems of medicament supply radius and cost, and are inconvenient to use in remote areas. The third type is to use low concentration SO 2 Absorbing or adsorbing and desorbing to obtain high-concentration SO 2 Returning to the acid making section to prepare sulfuric acid. For example, patent CN102743956A describes a process for preparing sulfuric acid from active coke desulfurization regeneration gas. However, activated coke (carbon) is not strictly an adsorbent, it will take part in the reaction to adsorb SO 2 By oxidation to SO 3 It is not favorable for subsequent treatment.
CN105251313A discloses a sulfur dioxide adsorption device, which comprises: the device comprises a silica gel drying column, a gas mixer, a pressure swing adsorption bed and a tail gas adsorption column, wherein the silica gel drying column comprises an air silica gel drying column and a sulfur dioxide silica gel drying column; the sulfur dioxide silica gel drying column is connected with the top of the pressure swing adsorption bed through a pipeline, and the air silica gel drying column is connected with the gas mixer and the bottom of the pressure swing adsorption bed through pipelines; the bottom of the pressure swing adsorption bed is connected with a tail gas adsorption column through a pipeline. The invention can also concentrate sulfur dioxide while treating sulfur dioxide pollution. The concentrated sulfur dioxide can be used for preparing acid or other purposes, and the activated carbon can be recycled. However, when SO is contained in the gas 2 The concentration is higher than 0.5%, the penetration time of the activated carbon column is short, and the adsorption-desorption needs to be frequently operated; in addition, activated carbon can contribute some of the SO 2 Conversion to SO 3 And is not favorable for subsequent treatment.
CN103920365A discloses a method for recovering nitrogen and sulfur dioxide in roasted pyrite furnace gas by variable-frequency and variable-pressure adsorption, which comprises the following process steps: after the furnace gas for roasting the pyrite is dedusted, purified, dried and cooled, dust particles and iron rust are removed by a refined sulfuric acid furnace gas filter made of 200 meshes of polytetrafluoroethylene; then the N is realized by a method of frequency conversion and pressure swing adsorption after deep fine dehydration, deoxidation and decarbonation of a fine dehydration tank 2 With SO 2 Is then passed throughCompressing or cooling, gas-liquid separating to obtain liquid SO 2 Separating the separated nitrogen and liquid SO 2 Bottling for industrial use; SO not separated by liquefaction 2 Then enters the cycle process of compression or cooling and gas-liquid separation to remove SO in the gas 2 Continuously separating. However, even if a variable-frequency and variable-pressure adsorption method is adopted, adsorption-desorption needs to be frequently operated due to the limited adsorption performance of the activated carbon; in addition, activated carbon can contribute some of the SO 2 Conversion to SO 3 And is not favorable for subsequent treatment.
Currently, the activated carbon (coke) materials widely used in industry have a high specific surface area and a pore structure, SO that the catalytic action of the metal active center on the activated carbon material can lead SO to be reacted by chemical reaction 2 Conversion to SO 3 Then further with H 2 O reaction to produce H 2 SO 4 Realizing SO in flue gas after alkaline washing 2 And (4) removing. But for high concentrations of SO 2 Flue gases, e.g. SO from S-Zorb flue gases of petroleum refining 2 Concentration of>0.5%, more preferably SO 2 Desorption is carried out after physical adsorption to realize SO 2 The adsorbent having the adsorption by chemical reaction is not suitable for use.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst containing SO 2 A method and apparatus for treating gas. The invention adopts a compression-adsorption process and combines a modified adsorption material to realize SO 2 High efficiency physical adsorption without frequent operation, SO 2 High recovery rate and good operation stability, and the purified gas meets the emission requirement.
The invention provides a process for preparing a compound containing SO 2 The gas treatment method comprises the following steps:
will contain SO 2 The gas is compressed in the compression unit and then enters the adsorption unit for adsorption, the adsorption material adopted by the adsorption unit is a modified zinc-based metal organic framework material, and desorption regeneration is performed after adsorption penetration.
In the invention, the modified zinc-based metal organic framework material is prepared by reacting zinc-based MOFs material in the presence of nitrogenAnd treating at 850-1150 deg.c for 5-10 hr. The zinc-based metal organic framework material can be at least one of MOFs-5, MOFs-74, ZIF series and the like, the ZIF series material can be at least one of ZIF-8, ZIF-20, ZIF-21 and the like, and MOFs-5 is preferable. The specific surface area of the zinc-based metal organic framework material is 850-1660 m 2 Per g, pore volume of 0.8-1.15 cm 3 (ii) in terms of/g. Furthermore, before the treatment, a certain amount of basic amino acid is doped for modification, such as at least one of lysine, arginine, histidine and the like, preferably histidine. The dosage of the amino acid is 0.01-5.0 percent of the mass of the metal organic framework material, and preferably 0.1-2.0 percent. The adsorption capacity of the modified zinc-based metal organic framework material is more than 2 times of that of the commercial active carbon.
In the present invention, the SO-containing compound 2 The gas can be waste gas or flue gas discharged from coal-fired power plants, metallurgical plants, petrochemical plants, etc., such as flue gas of coal-fired or oil-fired boilers, FCC regenerated flue gas, S-zorb adsorbent regenerated flue gas, etc., and SO in the flue gas 2 The volume concentration of (A) is generally 0.01% to 10%. According to the characteristics of the source of the waste gas, containing SO 2 The flue gas is pretreated by dedusting, cooling, dehydrating, drying and the like before compression.
In the invention, the compression unit mainly comprises a compressor and is used for compressing SO 2 The gas is compressed, the gauge pressure is controlled to be 0.1-1.0 MPaG, and the compressed gas enters an adsorption unit for adsorption.
In the invention, the adsorption unit consists of two or more than two adsorption towers and can alternately operate. The adsorption conditions were: the adsorption temperature is-10 to 40 ℃, preferably 5 to 30 ℃, and the space velocity of the adsorption volume is 100 to 1000h -1 The adsorption pressure is 0.1-1.0 MPa.
In the present invention, the concentration of the adsorption outlet is set to not higher than 50mg/m 3 The time is the penetration time, desorption is carried out after adsorption penetration, and the desorption can adopt methods such as heating regeneration, vacuum heat regeneration and the like, and preferably adopts the combination of vacuum regeneration and regular vacuum heat regeneration. The final absolute pressure of the regenerated adsorption tower is 3-8 KPa, the regeneration time is 1-10 hours, and the maximum absolute pressure does not exceed 70% of the adsorption time. The adsorption tower is subjected to multiple adsorption-desorptionThen, when the adsorption amount of the adsorbent is reduced to below 85% of the initial adsorption amount, carrying out vacuum thermal regeneration on the adsorption tower, taking nitrogen as a gas source, and maintaining the adsorption absolute pressure at 10-50 KPa and the temperature at 80-300 ℃. The obtained desorption gas is high-purity SO 2 Gas, can be used for requiring the use of SO 2 The gas is used for sulfur recovery device to prepare sulfur, oil refining waste lye acidification treatment and the like.
The invention also provides a method for treating the SO-containing gas 2 The gas treatment device mainly comprises a compression unit, an adsorption unit, a regeneration unit and the like, wherein the compression unit mainly comprises a compressor and is used for compressing waste gas; the adsorption unit mainly comprises two or more than two adsorption towers filled with modified zinc-based metal organic framework materials for SO 2 Adsorption of (3); the regeneration unit mainly comprises a vacuum pump, a nitrogen heater and the like and is used for desorbing and regenerating to obtain high-concentration SO 2。
The invention can realize SO by a compression-adsorption combined process and combined use of a modified adsorbent 2 High-efficiency physical adsorption and desorption, and can obtain SO with higher purity 2 Gas, SO 2 The recovery rate is high; and adsorption equipment does not need frequent switching, and operating stability is good, when realizing the discharge to reach standard of discharge gas, has reduced treatment cost, has good environmental protection benefit and economic benefits.
The invention adopts the modified metal organic framework material as the adsorption material, on one hand, SO can be avoided 2 Oxidation to SO 3 To realize SO 2 Exhibits more excellent SO than commercial activated carbon 2 Physical adsorption property. On the other hand, the modified zinc-based metal organic framework material has SO within the penetration time of 0.1-0.3 MPa 2 The adsorption capacity of the adsorption tower is more than 2 times that of commercial activated carbon and more than 1.6 times that of MOFs materials, so that the number and scale of the adsorption towers can be reduced, and the treatment cost is reduced. Adopts amino acid modified zinc-based metal organic framework material, is beneficial to SO 2 High-efficiency physical adsorption and rapid desorption of SO 2 After multiple cycles of adsorption-desorption, the adsorption capacityThe amount can be stabilized to more than 85 percent of the initial adsorption capacity, and the using effect is better.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention;
wherein, 1-pretreatment unit, 2-compressor, 3/4-adsorption tower, 5-SO 2 On-line detection, 6-vacuum pump, 7-SO 2 A buffer tank or a gas holder, 8-heater; 101-containing SO 2 Flue gas, 102-pretreated flue gas, 103-compressed flue gas, 104-adsorbed flue gas and 105-purified gas; 201-Desorption of gas, 202-evacuation of gas by vacuum pump, 203-Desorption of SO 2 204-nitrogen, 205-heated nitrogen, 206-pyrolysis suction cycle gas, 207-pyrolysis suction gas.
Detailed Description
The treatment method and the treatment effect of the present invention will be further described below by way of examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
The content of the metal element of the present invention was analyzed by the ICP method. SO in gas 2 The content was analyzed by an instrument (Emerson X-STREAM). The concentration of the adsorption outlet was set to 50mg/m 3 Time is penetration time, SO on the adsorption material 2 The adsorption capacity is calculated by the following formula:
in the formula: q is sulfur capacity, mg/g; q is the total flow of the mixed gas at the inlet, mL/min; c 0 Is an inlet SO 2 Concentration, mg/L; c i Is the ith sampling outlet SO 2 Concentration, mg/L; t is the ith sampling time, min; n is the sampling times when the adsorption reaches saturation or within a specified time; m is the adsorption material fillingAmount, g.
The treatment device of the invention is shown in figure 1 and mainly comprises a compressor 2, an adsorption tower 3/4, a vacuum pump 6 and SO 2 A buffer tank or gas holder 7, a nitrogen heater 8, etc. Containing SO 2 Firstly, the flue gas 101 passes through a pretreatment unit 1 to remove particles, water and the like in the flue gas, the pretreated flue gas 102 is compressed by a compressor 2, the compressed flue gas 103 enters an adsorption tower 3/4, the adsorption tower 3 and the adsorption tower 4 alternately operate, and the adsorbed flue gas 104 enters SO 2 On-line detection 5, when purifying gas SO 2 The concentration is less than 50mg/m 3 Switching to the adsorption tower 4 for adsorption, performing vacuum regeneration on the adsorption tower 3, starting the vacuum pump 6, introducing the desorption gas 201 into the vacuum pump 6, and introducing the vacuum pump exhaust gas 202 into the SO 2 Buffer tank or gas holder 7. After the adsorption tower is subjected to multiple adsorption-desorption operations, when the adsorption amount of the adsorbent is reduced to below 85% of the initial adsorption amount, the adsorption tower is subjected to vacuum thermal regeneration, the nitrogen 204 is heated by the heater 8, the heated nitrogen 205 and part of the pyrolysis absorption recycle gas 206 are mixed and enter the adsorption tower for desorption, and part of the pyrolysis absorption exhaust gas 207 and the pretreated SO-containing gas are desorbed 2 The gas mixture enters the compressor.
Example 1
Containing SO 2 The gas is catalytic cracking regenerated flue gas, and is pretreated by dust removal, cooling, dehydration and drying before compression, and SO in the treated waste gas 2 In a volume concentration of 0.05% to 0.2% (about 285 to 5700 mg/m) 3 ），O 2 The volume concentration of the flue gas is 3-5 percent, and the flue gas treatment capacity is 1000Nm 3 /h。
Preparing a modified zinc-based metal organic framework material: taking MOF-5 as a matrix, the specific surface area is 1655m 2 G, pore volume of 1.13cm 3 G, zn content 31.2%. Doping histidine accounting for 1.0 percent of the mass of MOFs-5, and treating for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
Will contain SO 2 Compressing the flue gas, controlling the gauge pressure to be 0.2-0.3MPaG, and then entering an adsorption unit for adsorption. The adsorption unit is filled with the modified zinc-based metal organic framework material. The adsorption conditions were: the adsorption temperature is 5-30 ℃, and the space velocity of the adsorption volume is not more than 600h -1 The adsorption pressure is 0.2-0.3MPa. The concentration of an adsorption outlet is 45mg/m 3 The time is used as the penetration time, and SO is arranged in the exhaust gas of the adsorption tower 2 And (3) performing online detection, wherein switching among the adsorption towers is controlled online, and the penetration time of a single adsorption tower is 50-60 h. Vacuum regeneration is adopted after the adsorption tower penetrates, the final absolute pressure of the adsorption tower is 3-5 KPa, and the regeneration time is 3-6 h. Relieving the SO 2 Into SO 2 The buffer tank is used for storing and conveying the sulfur to a sulfur recovery device for preparing sulfur. SO in the exhaust gas of the adsorption tower 2 The concentration is always lower than 50mg/m 3 。
After 2 months of operation, the adsorption tower passes about 28 times of adsorption-desorption cycles, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, the adsorption stability is good, and SO is recycled accumulatively 2 About 2.6t. During the operation period, vacuum thermal regeneration is carried out for 2 times, hot nitrogen is used as a gas source, the regeneration absolute pressure is 20-30 KPa, and the temperature is 160-180 ℃.
Example 2
Containing SO 2 The gas is S-zorb adsorbent regeneration flue gas, and is subjected to dust removal, cooling, dehydration and drying pretreatment before compression, and SO in the treated waste gas 2 The volume concentration of (A) is 2-5%, O 2 The volume concentration of the flue gas is less than 0.2 percent, and the flue gas treatment capacity is 500Nm 3 /h。
Preparing a modified zinc-based metal organic framework material: taking MOF-5 as a matrix, the specific surface area is 1655m 2 G, pore volume of 1.13cm 3 G, zn content 31.2%. Doping histidine accounting for 1.0 percent of the mass of MOFs-5, and treating for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
Will contain SO 2 The flue gas is compressed, the gauge pressure is controlled to be 0.4-0.5MPaG, and then the flue gas enters an adsorption unit for adsorption. The adsorption unit is filled with the modified zinc-based metal organic framework material, and the adsorption conditions are as follows: the adsorption temperature is 5-30 ℃, and the adsorption space velocity is not more than 300h -1 The adsorption pressure is 0.4-0.5MPa. The concentration of an adsorption outlet is 50mg/m 3 The exhaust gas of the adsorption tower is provided with SO as the penetration time 2 And (3) online detection, wherein switching among the adsorption towers is controlled online, and the penetration time of a single adsorption tower is about 2-6 h. Adsorption column breakthroughThen vacuum desorption is adopted, the final absolute pressure of the adsorption tower is 3-5 KPa, and the regeneration time is 1-3 h. Relieving the SO 2 Into SO 2 The buffer tank is used for storing and conveying the sulfur to a sulfur recovery device for preparing sulfur. SO in the exhaust gas of the adsorption tower 2 The concentration is always lower than 50mg/m 3 。
After 1 month operation, the adsorption tower passes about 170 times of adsorption-desorption cycles, the adsorption capacity of the adsorbent can be stabilized at more than 85% of the initial adsorption capacity, the adsorption stability is good, and SO is recycled accumulatively 2 About 32t. During the operation period, vacuum heat regeneration is carried out for 8 times, hot nitrogen is used as a gas source, the regeneration absolute pressure is 10-30 KPa, and the temperature is 220-250 ℃.
Example 3
Containing SO 2 The gas is catalytic cracking regenerated flue gas, and is pretreated by dust removal, cooling, dehydration and drying before compression, and SO in the treated waste gas 2 The volume concentration of (A) is 0.05% -0.2%, and O 2 The volume concentration of the flue gas is 3-5 percent, and the flue gas treatment capacity is 1000Nm 3 /h。
Preparing a modified zinc-based metal organic framework material: taking MOF-5 as a matrix, the specific surface area is 1655m 2 G, pore volume of 1.13cm 3 G, zn content 31.2%. Doping histidine accounting for 1.0 percent of the mass of MOFs-5, and treating for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
Will contain SO 2 Compressing the flue gas, controlling the gauge pressure to be 0.2-0.3MPaG, and then entering an adsorption unit for adsorption. The adsorption unit is filled with the modified zinc-based metal organic framework material. The adsorption conditions were: the adsorption temperature is 5-30 ℃, and the adsorption volume space velocity is not more than 500h -1 The adsorption pressure is 0.2-0.3MPa. The concentration of an adsorption outlet is 50mg/m 3 The exhaust gas of the adsorption tower is provided with SO as the penetration time 2 And (3) online detection, wherein switching among the adsorption towers is controlled online, and the penetration time of a single adsorption tower is 30-40 h. Vacuum desorption is adopted after the absorption tower penetrates, the final absolute pressure of the absorption tower is 3-5 KPa, and the regeneration time is 3-5 h. Relieving the SO 2 Into SO 2 The buffer tank is used for storing and conveying the sulfur to a sulfur recovery device for preparing sulfur. SO in the exhaust gas of the adsorption tower 2 The concentration is always lower than 50mg/m 3 。
After 1 month operation, the adsorption tower passes through about 20 times of adsorption-desorption cycles, the adsorption capacity of the adsorbent can be stabilized at more than 85% of the initial adsorption capacity, the adsorption stability is good, and SO is recycled accumulatively 2 About 2.8t. During the operation period, vacuum heat regeneration is carried out for 2 times, hot nitrogen is used as a gas source, the absolute pressure of regeneration is 20-30 KPa, and the temperature is 150-180 ℃.
Example 4
The same as example 1, except that: the preparation of the modified zinc-based metal organic framework material comprises the following steps: taking MOF-5 as a matrix, the specific surface area is 1655m 2 G, pore volume of 1.13cm 3 G, zn content 31.2%. And (3) doping lysine accounting for 1.0% of the MOF-5 by mass, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
The penetration time of a single adsorption tower is 45-55 h, and SO in the exhaust gas of the adsorption tower 2 The concentration is always lower than 50mg/m 3 . After 28 times of adsorption-desorption cycles, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, the adsorption stability is good, and SO is recycled accumulatively 2 About 2.5t. The desorbed adsorption column was thermally regenerated 2 times during the operation.
Example 5
The same as example 1, except that: the preparation of the modified zinc-based metal organic framework material comprises the following steps: taking MOF-5 as a matrix, the specific surface area is 1655m 2 G, pore volume of 1.13cm 3 G, zn content 31.2%. Doping arginine accounting for 1.0 percent of the MOF-5 by mass, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
The penetration time of a single adsorption tower is 44-53 h, and SO in the exhaust gas of the adsorption tower 2 The concentration is always lower than 50mg/m 3 . After 30 times of adsorption-desorption cycles, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, the adsorption stability is good, and SO is recycled accumulatively 2 About 2.5t. The desorbed adsorption column was thermally regenerated 2 times during the operation.
Example 6
The difference from example 1 is that: modified zinc-based metalThe preparation of the framework material comprises the following steps: ZIF-8 is taken as a substrate, and the specific surface area is 1150 m 2 Per g, pore volume 0.82 cm 3 G, zn content of 30.7 percent. And (3) doping arginine accounting for 1.0 percent of the mass of the ZIF-8, and carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
The penetration time of a single adsorption tower is 40-45 h, and SO in the exhaust gas of the adsorption tower 2 The concentration is always lower than 50mg/m 3 . After 31 times of adsorption-desorption cycles, the adsorption capacity of the adsorbent can be stabilized to more than 85% of the initial adsorption capacity, the adsorption stability is good, and SO is recycled accumulatively 2 About 2.4t. The desorbed adsorption column was thermally regenerated 3 times during the operation.
Example 7
The difference from example 1 is that: the preparation of the modified zinc-based metal organic framework material comprises the following steps: taking MOF-5 as a matrix, the specific surface area is 1655m 2 G, pore volume of 1.13cm 3 G, zn content 31.2%. Carbonizing for 6 hours at 1000 ℃ in the presence of nitrogen to obtain the modified zinc-based metal organic framework material.
The penetration time of a single adsorption tower is 30-35 h, and SO in the exhaust gas of the adsorption tower 2 The concentration is always lower than 50mg/m 3 . After 50 times of adsorption-desorption cycles, the adsorption capacity of the adsorbent can be stabilized at more than 85% of the initial adsorption capacity, the adsorption stability is good, and SO is recycled accumulatively 2 About 2.0t. The desorbed adsorption column was thermally regenerated 5 times during the operation.
Comparative example 1
The difference from example 1 is that activated carbon was used as the adsorbent. The penetration time of a single adsorption tower is 20-25 h, and 10 times of thermal regeneration is carried out on the adsorption tower after desorption during the operation period. After 70 times of adsorption-desorption circulation, the adsorption capacity of the adsorbent is about 70 percent of the initial adsorption capacity. In addition, there is a portion of SO 2 Oxidation to SO 3 Affecting subsequent processing.
Comparative example 2
The difference from example 1 is that MOF-5 is used as the adsorbent material. The penetration time of a single adsorption tower is 25-30 h, and 8 times of thermal regeneration is carried out on the adsorption tower after desorption during the operation period.After 65 adsorption-desorption cycles, the adsorption capacity of the adsorbent is about 75% of the initial adsorption capacity. In addition, there is a portion of SO 2 Oxidation to SO 3 Affecting subsequent processing.
Claims (13)
1. Containing SO 2 The gas treatment method is characterized by comprising the following steps: will contain SO 2 The gas is compressed in a compression unit and then enters an adsorption unit for adsorption, the adsorption material adopted by the adsorption unit is a modified zinc-based metal organic framework material, and desorption regeneration is carried out after adsorption penetration; the modified zinc-based metal organic framework material is modified by doping a certain amount of basic amino acid into a zinc-based MOFs material, wherein the basic amino acid is at least one of lysine, arginine and histidine, and is treated at 850-1150 ℃ for 5-10 hours in the presence of nitrogen; the zinc-based metal organic framework material is at least one of MOFs-5, MOFs-74 and ZIF series.
2. The method of claim 1, wherein: the zinc-based metal organic framework material is MOFs-5.
3. The method of claim 1, wherein: the basic amino acid is histidine.
4. A method according to claim 1 or 3, characterized in that: the dosage of the basic amino acid is 0.01-5.0% of the mass of the metal organic framework material.
5. The method of claim 4, wherein: the dosage of the basic amino acid is 0.1-2.0% of the mass of the metal organic framework material.
6. The method of claim 1, wherein: said SO-containing 2 The gas is waste gas or flue gas from coal-fired power plant, metallurgical plant or petrochemical plant, specifically flue gas of coal-fired or oil-fired boiler, FCC regeneration flue gas, S-zorb absorptionAt least one of the accessory agent regeneration flue gas and SO in the flue gas 2 The volume concentration of (A) is 0.01-10%.
7. The method according to claim 1 or 6, characterized in that: according to the characteristics of the source of the waste gas, the SO 2 The flue gas is subjected to dust removal, cooling, dehydration and drying pretreatment before compression.
8. The method of claim 1, wherein: the compression unit mainly comprises a compressor and is used for compressing SO 2 The gas is compressed, and the gauge pressure is controlled to be 0.1-1.0 MPaG.
9. The method of claim 1, wherein: the adsorption unit consists of two or more adsorption towers which alternately operate; the adsorption conditions were: the adsorption temperature is-10 to 40 ℃, and the space velocity of the adsorption volume is 100 to 1000h -1 The adsorption pressure is 0.1-1.0 MPa.
10. The method of claim 1, wherein: setting the concentration of the adsorption outlet not higher than 50mg/m 3 The time is the penetration time, desorption is carried out after the adsorption penetration, and the desorption adopts heating regeneration, vacuum regeneration or vacuum thermal regeneration.
11. The method of claim 10, wherein: the final absolute pressure of the regenerated adsorption tower is 3-8 KPa, the regeneration time is 1-10 hours, and the maximum absolute pressure does not exceed 70% of the adsorption time.
12. The method according to claim 10 or 11, characterized in that: after the adsorption tower is subjected to multiple times of adsorption-desorption, when the adsorption quantity of the adsorbent is reduced to be below 85% of the initial adsorption quantity, the adsorption tower is subjected to vacuum thermal regeneration, nitrogen is used as a gas source, the absolute adsorption pressure is maintained to be 10-50 KPa, and the temperature is 80-300 ℃.
13. For use in the SO-containing compositions as claimed in any of claims 1 to 12 2 Gas treatmentThe treatment device of the method is characterized by mainly comprising a compression unit, an adsorption unit and a regeneration unit, wherein the compression unit mainly comprises a compressor and is used for compressing the waste gas; the adsorption unit mainly comprises two or more adsorption towers filled with modified zinc-based metal organic framework materials for SO 2 Adsorption of (3); the regeneration unit mainly comprises a vacuum pump and a nitrogen heater and is used for desorbing and regenerating to obtain high-concentration SO 2 。
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| CN102389770A (en) * | 2011-09-28 | 2012-03-28 | 厦门大学 | Method for preparing flue gas adsorption desulfurizer |
| CN106457120A (en) * | 2014-04-22 | 2017-02-22 | 加利福尼亚大学董事会 | Cooperative chemical adsorption of acid gases in functionalized metal-organic frameworks |
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